Polymeric quaternary ammonium compounds and their uses

ABSTRACT

Novel polyquaternary ammonium compounds prepared from N,N&#39;-bis(dialkylaminoalkyl)ureas, hydrochloric acid, epichlorohydrin and tertiary amines are useful as microbicides, corrosion inhibitors, debonding agents, flocculants, softeners, anti-static agents, and demulsifiers.

This invention relates to novel polyquaternary ammonium compositionsincluding diquaternary ammonium compounds and to their uses asmicrobicides, corrosion inhibitors, debonding agents, flocculants,softeners, anti-static agents and demulsifiers.

The compositions have the structure ##STR1## R' is methyl, ethyl,propyl, hydroxyethyl or hydroxypropyl; characterized in that R' and R"are identical when R' is an ethyl, propyl, hydroxyethyl or hydroxypropyland when R' is methyl, R" is independently methyl or an alkyl groupcontaining 5 to 22 carbon atoms having 0 to 2 carbon to carbon doublebonds, cyclohexyl, benzyl or phenyl; further characterized in that R'and R" may form a pyridyl group; Q is ##STR2## R'" is a lower alkylgroup, m is 0 or a number from 1 to 100, n is 2 or 3, and p varies from2 to 12.

All of the products of this invention are derived fromN,N'-bis(dialkylaminoethyl)urea or N,N'-bis(dialkylaminopropyl)urea inwhich the alkyl groups are lower alkyl, such as methyl, ethyl andpropyl, which hereinafter will sometimes be referred to as "ureadiamine". The preparation of N,N'-bis(dimethylaminopropyl)urea fromdimethylaminopropylamine and urea is described in Example 1 of U.S. Pat.No. 4,157,388. Other diamines which can be reacted with urea includedimethylaminoethylamine, diethylaminoethylamine,diethylaminopropylamine, and other lower dialkylaminoethylamines anddialkylaminopropylamines.

A number of reaction sequences can be used, starting with the "ureadiamines" to produce the novel products of this invention. These aredescribed in the following:

1. In order to prepare the simplest di-quaternary ammonium compounds ofthis invention, one mole of the "urea diamine" is reacted with two molesof hydrochloric acid to make the diamine dihydrochloride which is thenreacted with two moles of epichlorohydrin to produce abis(chlorohydrin). This reaction is usually run in water or lower alkylalcohols at a temperature varying from 50° to 110° C. WhenN,N'-bis(dimethylaminopropyl)urea is used in this sequence, thefollowing compound, which we refer to as bis(chlorohydrin)A, isproduced: ##STR3##

2. The bis(chlorohydrins) can be reacted in other ways to produceproducts of this invention. In the first type of reaction, one mole ofthe bis(chlorohydrin) is reacted with one or two moles of tertiary aminein such a manner as to form one or two additional quaternary ammoniumgroups at the extremities of the bis(chlorohydrins). The tertiary aminesused for this reaction have the structure: ##STR4## wherein R' ismethyl, ethyl, propyl, hydroxyethyl or hydroxypropyl characterized inthat R' and R" are identical when R' is ethyl, propyl, hydroxyethyl orhydroxypropyl. When R' is methyl, R" is independently methyl or an alkylgroup containing 5 to 22 carbon atoms having 0 to 2 carbon to carbondouble bonds, cyclohexyl, benzyl or phenyl. R' and R" may also form apyridyl group. N-Methylpiperidine may also be used to cap thebis(chlorohydrins).

3. The bis(chlorohydrins exemplified by bis(chlorohydrin)A can also bereacted with equi-molar quantities of ditertiary amines to form novelpolyquaternary ammonium products, known as ionene polymers. Theditertiary amines are selected from ##STR5## andN,N'-dimethylpiperazine, where Q is ##STR6## wherein p is an integervarying from 2 to 12 and n is either 2 or 3.

4. Other polymeric quaternary ammonium products of this invention areprepared by reacting X moles of the bis(chlorohydrin) at an elevatedtemperature in the presence of water with X-1 moles of the ditertiaryamines already described in reaction type 3 above. We have foundsuitable reaction temperatures and times may vary from about 80° to 105°C. and from 1 to 30 hours. As used herein, X is an integer varying from2 to 101. The molecular weight of the precursor is calculated bymultiplying X times the molecular weight of the bis(chlorohydrin) usedand adding X-1 times the molecular weight of the second ditertiaryamine.

5. The products produced in reaction type 4 have reactive chlorine atomsat both extremities and can be reacted further with one or two moles ofthe monotertiary amines described hereinbefore in reaction type 2 in thepresence of water or a solvent at a temperature varying from about 25°to 110° C. for a period varying from about 1 to 30 hours.

Suitable solvents in all of the reactions are water or water-solublelower alcohols and other polar compounds.

The reactions described in reaction types 3 and 4 involve the reactionof an α,ω-ditertiary amine with an α,ω-dihalogenated alkyl compound.This reaction is known in the chemical literature as a MenschutkinReaction and is used to prepare relatively low molecular weight polymerswhich are polymeric quaternary ammonium compounds known as ionenepolymers. The molecular weights of these linear ionenes are generallyabout 50,000 or less.

The polymer chain length can be controlled by using the method ofmanufacture described in reaction type 4 of this invention. When twomoles of the α,ω-dihalo compound (X moles) are reacted with one mole(X-1 mole) of the ditertiary amine, a polymer is formed. When thedesignation P is used for the dihalo compound and O for the ditertiaryamine, the polymer could then be designated P-O-P. When 5 moles of P and4 moles of O are reacted, the precursor then is P-O-P-O-P-O-P-O-P. Thesame general scheme can be used to a maximum of about 101 for P and 100for O. Regardless of the number of moles of P and O used, there will bea halogen at either end of the precursor polymer. This precursor is thenreacted with a monotertiary amine as described in reaction type 5 to"cap" the ionene with additional quaternary ammonium groups. The natureof the tertiary amine and the length of the precursor polymer chain willdetermine the properties of the polymers of this invention and allow forthe variation of hydrophilic and hydrophobic properties.

The mono-tertiary amines which may be used to cap the bis(chlorohydrins)as described in reaction types 2 and 5 may include aliphatic, alicyclic,alkylaromatic, aromatic and heterocyclic amines. The aliphatic groupsmay contain one or more carbon to carbon double bonds, and may besubstituted with hydroxyl groups. Examples of these amines aretrimethylamine, triethylamine, N,N-dimethylstearylamine,N,N-dimethyloleylamine, N,N-dimethylcaprylamine,N,N-dimethyllaurylamine, N,N-dimethylmyristylamine,N,N-dimethylpalmitylamine, methyldistearylamine, didecylmethylamine,methyldicocoamine, methyl dihydrogenated tallow amine,1-chloro-3-(dimethylamino)-2-propanol, N,N-dimethylaniline, pyridine,N,N-dimethylbenzylamine, triethanolamine, 2-(dimethylamino)ethanol,triisopropanolamine, N,N-bis(1-methylethyl)-2-propanamine,N,N-dimethylcyclohexylamine and N-methylpiperidine.

The ditertiary amines reacted with the bis(chlorohydrins) as describedin reaction types 3 and 4 includeN,N,N',N'-tetramethyl-α,ω-alkanediamines wherein the alkane groupcontains 2 to 12 carbon atoms exemplified byN,N,N',N'-tetramethylethylenediamine,2,2'-oxybis(N,N-dimethylethanamine),N,N,N',N'-tetramethyl-2-butene-1,4-diamine,1,3-bis(dimethylamino)-2-propanol, 1,4-dimethylpiperazine,N,N'-bis(dialkylaminoethyl)urea, and N,N'-bis(dialkylaminopropyl)ureawherein the alkyl groups are lower alkyl groups.

The compositions of this invention are useful in the control ofslime-forming and other microorganisms, particularly in industrialprocesses involving water and substances that are normally susceptibleto microbiological degradation or deterioration in the presence ofwater, in which the growth and proliferation of such microorganismsinterfere in the process itself or affect the quality or character ofthe resulting product.

Most microbiological problems associated with industrial and commercialcooling and process water systems are caused by a mixed microfloratypically composed of algae, bacteria, and fungi. These microorganismscan cause the formation of biological slime, plugging and fouling,deterioration of wood, and microbiologically induced corrosion.

The compounds of this invention have been found to be extremelyeffective in controlling microorganisms, and the concentrations whichare suitable for the control of said microorganisms vary from 0.5 to 500ppm based on the weight of the aqueous system or water being treated.

The corrosion of metals in water is an electrochemical process thatoccurs because of difference in electrical potential between points onthe metal surface or between two metal surfaces. This difference inpotential between points on the metal surface can be due to severalfactors such as: differences in composition, differences in crystalsize, crystal orientation, discontinuous oxide film due to air or heattreatment, stress, superficial foreign matter, inclusions of dissimilarmaterial and alloys, differences in the concentration of dissolvedoxygen as compared with another, and the contact of dissimilar metals.For control of corrosion in aqueous systems concentrations of 0.5 to 500ppm based on the weight of water treated are suitable with a preferredconcentration range of 0.5 to 50 ppm. The products of this invention maybe used alone or in combination with other known corrosion inhibitors.

Cellulose pulp fiber which has been formed in the conventional manner asa pulp sheet or board on a papermaking machine is normally verydifficult to fiberize. However, it can be modified with debondingcompositions so that the resulting sheet or board is easily fiberized bymechanical means. The compositions of this invention are used in a fiberdebonding process involving the impregnation of cellulose pulp fiber tofacilitate the defiberization of pulp. For this purpose, the products ofthis invention are used in amounts varying from 0.1 to 2.0 parts per 100parts of cellulose pulp fiber based on the dry weight of the fiber. Inaddition to serving as debonding agents, the products of this inventionare also used to soften paper and other cellulosic products includingtextiles. When softening is desired, the concentration used varies from0.1 to 1.0 parts per 100 parts of textile fabric, paper or cellulosicpulp based on the dry weight of the material treated.

The composition of our invention are also useful as flocculants in theclarification of incoming water supplies and industrial and municipaleffluents. In particular, the new compositions may be used in recoveryof the valuable materials remaining in the process waters of pulp andpaper manufacture, thereby also alleviating the pollution problem of theindustry. These compositions can also be used to remove any solidparticulate matter remaining in the water before it is discharged, eventhough such matter is not of a character suitable for use but must bedisposed of by microbiological decomposition or combustion or buried ina sanitary fill. They may be used in the treatment of incoming watersupplies as a supplement to low-cost alum, thus achieving a reduction ofprocess time in addition to the desired degree of completeness in theremoval of finely divided solids. Similar principles apply to theremoval of particles solid matter from water discharges in industrial ormunicipal effluents. Useful concentrations for this purpose may varyfrom as low as 0.1 ppm based on the total weight of water andparticulate matter to as high as 25 ppm on the same basis with apreferred range from 0.5 to 5 ppm.

The accumulation of static electricity in a wide range of modernfabrics, especially when dried in a mechanical clothes dryer, causes thematerial to cling and become difficult to manage. The products of thisinvention have been found to be effective in eliminating staticelectricity on fibers such as dynel, dacron, orlon, nylon, acetate,wool, and also on such plastic materials as polystyrene. For these uses,the concentrations of these products vary from 0.125% to 0.5%.

Most of the petroleum produced in the United States contains water,usually as a stable emulsion of the water in oil. Although somewater-free oil may be produced in the Middle East, it is reasonable toestimate that 60 to 70% of the world production must be dehydratedbefore being shipped to the refineries. Emulsions of crude oil in waterare generally broken by the use of chemicals known as demulsifiers. Theactual separation of the oil in water takes place in special equipmentwhich allows the water to separate from the oil by gravity assisted byheat. The products of this invention are excellent demulsifiers and canbe used to break both oil-in-water or water-in-oil emulsions atconcentrations of 0.5 to 500 ppm based on the weight of the emulsion.

It is, therefore, a principal object of our invention to provide novelpolyquaternary ammonium compositions.

It is another object of our invention to provide methods for controllingthe growth of algae, bacteria, and fungi in aqueous systems.

It is yet another object of this invention to provide methods offlocculating impurities in water and methods of improving processing ofwastes.

It is yet another object of our invention to provide methods ofseparating crude petroleum from water.

These and other objects and advantages of the novel compositions andmethods of this invention will become apparent as the descriptionproceeds.

In order to disclose the nature of the present invention still moreclearly, the following illustrative examples will be given. It is to beunderstood, however, that the invention is not to be limited to thespecific conditions or details set forth in these examples exceptinsofar as such limitations are specified in the appended claims.

EXAMPLE 1 Preparation of 1,3-bis(dimethylaminoethyl)urea

A two-liter, four-necked reaction flask fitted with a reflux condenser,mechanical stirrer, thermometer and a gas inlet tube was charged with507.7 g (5.76 moles) of dimethylaminoethylamine and 172.9 g (2.88 moles)of urea. While stirring and heating, N₂ was bubbled through the reactionmass carrying NH₃ gas out and into a sulfuric acid trap. Reflux began at110° C. Heating was continued for approximately 15 hours as thetemperature rose to 214° C. Analysis showed that 5.8 moles of thesulfuric acid had been neutralized by the ammonia and the equivalentweight of the product was found to be 101.8 (Theoretical=101.1). Theproduct was a clear light amber color.

EXAMPLE 2 Preparation of Bis(chlorohydrin) A ##STR7##

A five-liter, four-necked reaction flask fitted with a reflux condenser,mechanical stirrer, thermometer and a dropping funnel was charged with996.6 g (4.0 moles) of 1,3-bis(dimethylaminopropyl)urea of 92.5 percentpurity. This compound was prepared by the method described in U.S. Pat.No. 4,157,388. The contents of the flask were chilled by immersion intoan ice-water bath, and 788.4 g (8.0 moles) of 37 percent hydrochloricacid was added at such a rate as to keep the temperature below 48° C. Tothe well-agitated 1,3-bis(dimethylaminopropyl)urea dihydrochloridesolution so obtained, 740.0 g (8.0 moles) of epichlorohydrin was addedslowly, taking care that the temperature did not exceed 48° C. Afterthis addition was completed, the solution was kept at 45°-48° C. forone-half hour and then heated at 70° C. for another 30 minutes. A 77.3percent aqueous solution of the title compound was obtained.

EXAMPLE 3 Preparation of Bis(chlorohydrin) B ##STR8##

A one-liter, four-necked reaction flask fitted with a reflux condenser,mechanical stirrer, thermometer and a dropping funnel was charged with101.1 g (0.5 mole) of 1,3-bis(2-dimethylaminoethyl)urea prepared inExample 1 and 167.7 g of water. The solution was chilled by immersion inan ice-water bath, and 98.7 g (1.0 mole) of 37 percent hydrochloric acidwas added at such a rate as to keep the temperature below 48° C. To thewell-agitated 1,3-bis(2-dimethylaminoethyl)urea dihydrochloride solutionso obtained, 92.5 g (1.0 mole) of epichlorohydrin was added slowly,taking care that the temperature did not exceed 48° C. After thisaddition was completed, the solution was kept at 45°-48° C. for 30minutes and then heated at 70° C. for another 30 minutes. A 50 percentaqueous solution of the title compound was obtained.

EXAMPLEs 4 TO 9

Various quantities of the 77.3 percent aqueous solution ofbis(chlorohydrin) A prepared in Example 2 were reacted at refluxtemperatures in water with a number of tertiary amines at a ratio of twomoles of tertiary amine to one mole of the bis(chlorohydrin) A. Thesereactions are included in Table 1.

                  TABLE 1                                                         ______________________________________                                                                  Time of  Solids                                             Tertiary          Reaction Content                                    Example Amine             Hours    Percent                                    ______________________________________                                        4       N,N--dimethylcaprylamine                                                                        6        50                                         5       N,N--dimethylmyristylamine                                                                      6        50                                         6       N,N--dimethylstearylamine                                                                       6        25                                         7       N--methyldistearylamine                                                                         8        15                                         8       N--methylpiperidine                                                                             2        50                                         9       triethanolamine   5        40                                         ______________________________________                                    

EXAMPLES 10 TO 14

Various quantities of the 50 percent aqueous solution ofbis(chlorohydrin) B prepared in Example 3 were reacted at refluxtemperatures in water with a number of tertiary amines at a ratio of twomoles of tertiary amine to one mole of the bis(chlorohydrin) B. Thesereactions are included in Table 2.

                  TABLE 2                                                         ______________________________________                                                                  Time of  Solids                                             Tertiary          Reaction Content                                    Example Amine             Hours    Percent                                    ______________________________________                                        10      N,N--dimethylcaprylamine                                                                        6        50                                         11      N,N--dimethylmyristylamine                                                                      6        50                                         12      N,N--dimethylstearylamine                                                                       6        25                                         13      N--methyldistearylamine                                                                         8        15                                         14      triethanolamine   5        40                                         ______________________________________                                    

EXAMPLE 15 Reaction of bis(chlorohydrin) A with two moles ofN,N,N',N'-tetramethylethylenediamine

Into a one-liter, four-necked reaction flask equipped with a refluxcondenser, a mechanical stirrer, thermometer, and a dropping funnel wereplaced 157.9 g (0.25 mole) of 77.3 percent solution of bis(chlorohydrin)A prepared in Example 2 and 99.7 g of water. This solution was heated tobetween 40° and 50° C. while agitating by means of the mechanicalstirrer. Then 83. g (0.5 mole) of a 70 percent aqueousN,N,N',N'-tetramethylethylenediamine was slowly introduced. Theresulting mixture was heated at reflux temperature for 2 hours and theproduct was obtained as a clear, dark amber-colored solution containing50 percent solids.

EXAMPLE 16 Reaction of bis(chlorohydrin) A with two moles of1,4-dimethylpiperazine

Similarly to the procedure given in Example 15, 157.9 g (0.25 mole) of a77.3 percent aqueous solution of bis(chlorohydrin) A prepared in Example2 in 76.1 g of water was treated with 124.4 g (0.5 mole) of a 45.9percent aqueous solution of 1,4-dimethylpiperazine. The polyquaternaryammonium chloride product, containing tertiary amine end groups wasobtained in a 50 percent concentration as a dark amber colored solution.

EXAMPLES 17 TO 22 Reactions of bis(chlorohydrin) A with ditertiaryamines at 1 to 1 mole ratios

Various quantities of the 77.3 percent aqueous solution ofbis(chlorohydrin) A prepared in Example 2 were reacted at refluxtemperature in water with a number of ditertiary amines at a mole ratioof 1 to 1. These reactions are listed in Table 3.

                  TABLE 3                                                         ______________________________________                                                                  Time of  Solids                                                               Reaction Content                                    Example Ditertiaryamine   Hours    Percent                                    ______________________________________                                        17      N,N,N',N'--tetramethyl-                                                                         3        50                                                 ethylenediamine                                                       18      1,4-dimethylpiperazine                                                                          8        50                                         19      2,2'-oxybis(N,N--dimethyl-                                                                      2        50                                                 ethanamine                                                            20      N,N,N',N'--tetramethyl-2-                                                                       2        50                                                 butene-1,4-diamine                                                    21      1,3-bis(dimethylamino)-                                                                         2        50                                                 2-propanol                                                            22      N,N'--bis(dimethylamino-                                                                        6        50                                                 propyl)urea                                                           ______________________________________                                    

EXAMPLES 23 AND 24 Reactions of bis(chlorohydrin) B with ditertiaryamines at 1 to 1 mole ratio

The procedure used for Examples 17 to 22 was followed withbis(chlorohydrin) B and N,N,N',N'-tetramethylethylenediamine (Example23) and N,N'-bis(dimethylaminopropyl)urea (Example 24). The reactiontimes were 3 and 6 hours respectively and the solids concentration ofthe products prepared was 50 percent.

EXAMPLES 25 TO 31 Reactions of X moles of bis(chlorohydrin) A with X-1moles of ditertiary amines

Various quantities of the 77.4 percent aqueous solution ofbis(chlorohydrin) A prepared in Example 2 and various ditertiary amineswere refluxed for several hours in water while being vigorously stirred.The reaction products, polyquaternary ammonium salts, containing ureamoieties, were obtained as solutions having total solids content asindicated in Table 4.

                  TABLE 4                                                         ______________________________________                                        Ex-  Bis(chloro-                      Solids                                  am-  hydrin) A                  Amine Content                                 ple  Moles     Ditertiary Amine Moles Percent                                 ______________________________________                                        25   2         N,N,N',N'--tetramethyl                                                                          1    50                                                     ethylenediamine                                                26   26        N,N,N',N'--tetramethyl                                                                         25    50                                                     ethylenediamine                                                27   101       N,N,N',N'--tetramethyl                                                                         100   50                                                     ethylenediamine                                                28   10        1,3-bis(dimethylamino)-                                                                         9    50                                                     2-propanol                                                     29   45        1,3-bis(dimethylamino)-                                                                        44    50                                                     2-propanol                                                     30   26        N,N'--bis(dimethylamino-                                                                       25    50                                                     propyl) urea                                                   31   75        N,N'--bis(dimethylamino-                                                                       74    50                                                     propyl) urea                                                   ______________________________________                                    

EXAMPLES 32 TO 37 Reactions of X moles of bis(chlorohydrin) B with X-1moles of ditertiary amines

Various quantities of the 50 percent aqueous solution ofbis(chlorohydrin) B prepared in Example 3 and various ditertiary amineswere refluxed for several hours in water or mixtures of isopropanol andwater while being vigorously stirred. The poly(quaternary ammonium)saltsobtained as solutions having total solids content as indicated in Table5.

                  TABLE 5                                                         ______________________________________                                        Ex-  Bis(chloro-                      Solids                                  am-  hydrin) A                  Amine Content                                 ple  Moles     Ditertiary Amine Moles Percent                                 ______________________________________                                        32   2         N,N,N',N'--tetramethyl                                                                         1     50                                                     ethylenediamine                                                33   50        N,N,N',N'--tetramethyl                                                                         49    50                                                     ethylenediamine                                                34   2         1,3-bis(dimethylamino)-                                                                        1     50                                                     2-propanol                                                     35   40        1,3-bis(dimethylamino)-                                                                        39    50                                                     2-propanol                                                     36   2         N,N'--bis(dimethylamino-                                                                       1     50                                                     propyl) urea                                                   37   30        N,N'--bis(dimethylamino-                                                                       29    50                                                     propyl) urea                                                   ______________________________________                                    

EXAMPLES 38 TO 49 Reactions of bis(chlorohydrins) with tertiary amines

The new bis(chlorohydrins) prepared in Examples 25 to 30 frombis(chlorohydrin) A and ditertiary amines were capped with quaternaryammonium groups by reacting one mole of the said bis(chlorohydrin) withtwo moles of mono tertiary amines. These reactions were run at refluxusing solvents such as water, alcohols or mixtures of water and alcoholsas described in Table 6.

                                      TABLE 6                                     __________________________________________________________________________         Chlorohydrin    Time at           Solids                                      used            reflux            Content                                Example                                                                            Example                                                                              Solvent  Hours                                                                              Tertiaryamine                                                                              Percent                                __________________________________________________________________________    38   25     water    4    N,N--dimethyllauryl-                                                                       25                                                               amine                                               39   25     water    5    N,N--dimethylmyristyl-                                                                     25                                                               amine                                               40   25     water    5    N,N--dimethylpalmityl-                                                                     25                                                               amine                                               41   25     water/   8    N,N--dimethylstearyl-                                                                      25                                                 propylene glycol                                                                            amine                                               42   25     water    4    triethanolamine                                                                            50                                     43   26     water/   6    N,N--dimethyllauryl-                                                                       25                                                 isopropanol   amine                                               44   26     water/   6    N,N--dimethylmyristyl-                                                                     25                                                 isopropanol   amine                                               45   26     water/   8    N,N--dimethylpalmityl-                                                                     25                                                 propylene glycol                                                                            amine                                               46   26     water/   12   N,N--dimethylstearyl-                                                                      25                                                 propylene glycol                                                                            amine                                               47   26     water    4    triethanolamine                                                                            50                                     48   27     water/   6    N,N--dimethyllauryl-                                                                       25                                                 isopropanol   amine                                               49   27     water    4    triethanolamine                                                                            50                                     __________________________________________________________________________

EXAMPLE 50

The effect of the novel polymeric quaternary ammonium compositionsdescribed in the preceding examples on the percentage kill of thebacterium Enterobacter aerogenes was determined using the methoddescribed in U.S. Pat. No. 2,881,070, with the modification described inU.S. Pat. No. 4,054,542. The results are included in Table 7.

                  TABLE 7                                                         ______________________________________                                                    Concentration in part per million                                             required for 80 percent kill or greater                                       of Enterobacter aerogenes in a basal                              Ionene polymer                                                                            salt substrate after 18 hours contact                             from examples                                                                             pH 6.0-6.5 pH 7.0-7.5                                                                              pH 8.0-8.5                                   ______________________________________                                        4           --         --        0.1                                          5           --         --        0.1                                          7           --         --        0.1                                          8           0.1        0.1       0.3                                          17          0.1        0.1       0.3                                          18          0.4        0.5       0.4                                          25          0.1        0.1       0.1                                          ______________________________________                                    

EXAMPLE 51

The effect of some of the novel polymeric quaternary ammoniumcompositions described in the preceding examples on the inhibition ofthe algae Chlorella pyrenoidosa, Chlorococcum hypnosporum, andPhormidium inundatum was determined using the procedure described inExample 2 of U.S. Pat. No. 3,771,989. The results are included in Table8. Observations of growth were made after 28 days on the basis of thefollowing Key:

4=Excellent

3=Good

2=Poor

1=Very poor, scant, questionable

0=No growth

                  TABLE 8                                                         ______________________________________                                                 Concentration in parts per                                                    million required for inhibition                                               of growth after 28 days                                              Ionene polymer                                                                           Chlorella  Chlorococcum                                                                              Phormidium                                  from examples                                                                            pyrenoidosa                                                                              hypnosporum inundatum                                   ______________________________________                                        10         --         --          1.0                                         11         --         --          2.0-4.0                                     12         --         --          6.0                                         17         1.0-3.0    2.0         3.0                                         25         --         --          1.0-2.0                                     31         --         --          2.0                                         ______________________________________                                    

EXAMPLE 52

The ionene-type polymers of this invention were used in the treatment ofwet bleached pine kraft pulp in the form of an aqueous slurry with apulp consistency of 0.5 percent. Handsheets were formed from the pulp ona laboratory handsheet machine to produce 20 cm×20 cm pulp sheets withbasis weights of 120 g/m². After the sheets were formed, pressed, anddried by the standard procedure, the bonding effect was evaluated bydetermining the fiber to fiber internal bonding strength of these sheetsby means of a Scott Internal Bond Tester as described in TAPPI UM-403.The debonding effect was expressed as a percentage factor calculated asfollows: ##EQU1##

Thus, the untreated pulp would have an Internal Bond Factor of 100 anddebonded pulp would have an Internal Bond Factor below 100. The higherthis factor, the greater the degree of bonding achieved.

Table 9 shows the results obtained with the ionene polymers when theywere evaluated by the indicated test method. Treatment rates are inweight percent based on the dry weight of pulp.

                  TABLE 9                                                         ______________________________________                                                    Treatment Rate                                                                            Internal Bond                                         Example     Percent     Factor                                                ______________________________________                                         7          0.5          71                                                   17          0.5         115                                                   25          0.5         110                                                   ______________________________________                                    

The invention having thus been described, what is claimed and desired to be secured by Letters Patent is:
 1. The polyquaternary ammonium compositions having the structure ##STR9## R' is methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl; characterized in that R' and R" are identical when R' is an ethyl, propyl, hydroxyethyl or hydroxypropyl and when R' is methyl, R" is independently methyl or an alkyl group containing 5 to 22 carbon atoms having 0 to 2 carbon to carbon double bonds, cyclohexyl, benzyl or phenyl; further characterized in that R' and R" may form a pyridyl group; Q is ##STR10## R'" is a lower alkyl group, m is 0 or a number from 1 to 200, n is 2 or 3, and p varies from 2 to
 12. 2. The polyquaternary ammonium composition of claim 1 wherein A is chlorine, B is ##STR11## and m is
 0. 3. The polyquaternary ammonium composition of claim 1 wherein ##STR12## and m is
 0. 4. The polyquaternary ammonium composition of claim 1 wherein A is ##STR13## and m is
 0. 5. The polyquaternary ammonium composition of claim 1 wherein A is ##STR14## and m is
 0. 6. The polyquaternary ammonium composition of claim 1 wherein A is chlorine ##STR15## and m varies from 1 to
 200. 7. The polyquaternary ammonium composition of claim 1 wherein A is chlorine or ##STR16## and m varies from 1 to
 200. 8. The polyquaternary ammonium composition of claim 1 wherein A is chlorine, B is ##STR17## and m varies from 1 to
 200. 9. The polyquaternary ammonium composition of claim 1 wherein A is chlorine, ##STR18## and m varies from 1 to
 200. 10. The polyquaternary ammonium composition of claim 1 wherein A is ##STR19## and m varies from 1 to
 200. 11. The polyquaternary ammonium composition of claim 1 wherein A is ##STR20## and m varies from 1 to
 200. 